CN104307558B - A kind of it is catalyzed triose catalyst being isomerized to lactic acid and lactate and its preparation method and application - Google Patents
A kind of it is catalyzed triose catalyst being isomerized to lactic acid and lactate and its preparation method and application Download PDFInfo
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- CN104307558B CN104307558B CN201410467259.7A CN201410467259A CN104307558B CN 104307558 B CN104307558 B CN 104307558B CN 201410467259 A CN201410467259 A CN 201410467259A CN 104307558 B CN104307558 B CN 104307558B
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Abstract
The invention belongs to catalyst technical field, be catalyzed triose catalyst being isomerized to lactic acid and lactate and preparation method thereof particularly to a kind of.Described catalyst is introduced metal ion Sn by the USY molecular sieve of FAU configuration after acid treatment dealuminzation2+Or Sn4+Obtain.The invention provides and a kind of just can be catalyzed the catalyst that triose Efficient Conversion is lactic acid or lactate in room temperature, catalyst can be reused, and has excellent isomerization activity and selectivity.
Description
Technical field
The invention belongs to catalyst technical field, be isomerized to urging of lactic acid and lactate particularly to a kind of triose that is catalyzed
Agent and its preparation method and application.
Background technology
Lactic acid (2 hydroxy propanoic acid) and lactate are widely used in food, cosmetics, chemicals and pharmaceuticals industry, this
Outward, lactic acid is also used to synthesising biological degradation plastic PLA, it is contemplated that the year two thousand twenty, and the market demand of PLA is up to three
Million tons.Lactic acid can be prepared through chemical synthesis by hydrogen cyanide and acetaldehyde, but, owing to breast cyanogen hydrolysis need to consume substantial amounts of sulfuric acid
(1040 kg/t), and hydrogen cyanide has severe toxicity, causes environmental protection pressure big, limits the application of the method.Along with oil etc.
The minimizing day by day of non-renewable resources total amount, people increasingly pay attention to utilizing renewable resource to prepare the high added values such as lactic acid
Product.
Biomass resource is renewable resource the abundantest on the earth, and bio oil includes vegetable oil and animal fat, can lead to
Cross ester exchange reaction and prepare biodiesel.But produce substantial amounts of by-product glycerin during biological diesel oil refining, often produce 10 kg
Biodiesel just has 1 kg glycerine to generate, and forms international glycerol market huge impact and causes glycerine price drastically to decline.
Develop the chemical products with high added-value with glycerine as raw material and bio-fuel has become inexorable trend, as glycerine can be obtained by oxidation
To triose (1,3-Dihydroxyacetone and glyceraldehyde), triose can get lactic acid and the lactate of high added value through isomerization reaction.
Triose tautomerizes to lactic acid or lactate is often carried out under acid catalysis, and relative to homogeneous acid catalyst, solid acid has and is easily isolated
The advantage reclaimed and can be recycled.The solid acid catalyst activity currently reported is relatively low, it usually needs higher
At a temperature of (> 80oC) preferable lactic acid or lactate yield can be obtained, cause energy consumption higher, be unfavorable for industrialized production.
Summary of the invention
It is an object of the invention to provide a kind of triose that is catalyzed and be isomerized to lactic acid and the catalyst of lactate and preparation side thereof
Method and application, described catalyst can realize being catalyzed triose under mild conditions and be isomerized to lactic acid and lactate, reduce
Energy consumption, it is simple to industrial applications.
The technical solution used in the present invention is as follows:
A kind of triose that is catalyzed is isomerized to the catalyst of lactic acid and lactate, by the USY molecular sieve of FAU configuration through acid treatment
Metal ion Sn is introduced after dealuminzation2+Or Sn4+Obtain.
Preferably, for the acid of acid treatment dealuminzation selected from one or more mixture following: nitric acid, hydrochloric acid, grass
Acid, citric acid, ethylenediamine tetra-acetic acid.
After acid treatment dealuminzation in USY molecular sieve sial atomic molar ratio not less than 40.
Concrete, can use but be not limited to use following methods to carry out acid treatment: acid is configured to the aqueous solution, according to often
The ratio adding 1g in 20-30ml aqueous acid adds USY molecular sieve, and under stirring condition, 80-90 DEG C processes 6-8 hour.
Solid liposome nanoparticle method is used to introduce metal ion Sn2+Or Sn4+。
Introduce metal ion Sn2+Or Sn4+Use precursor be preferably its halide, acetate, sulfate, oxalates or
Organotin.
Metal ion Sn2+Or Sn4+Introduction volume is the 0.1-5.0% of molecular sieve quality.
Catalyst of the present invention in use, described catalyst is used for triose conversion in water or alcohol prepare lactic acid or
Lactate, reaction temperature is 20-90 DEG C, and the time is 0.5-24 h, and triose mass percentage concentration in water or alcohol is 2-30%.
Catalyst provided by the present invention can under the conditions of room temperature (25 DEG C), with water or alcohol such as methyl alcohol, ethanol, propyl alcohol,
The alcohol such as butanol are solvent, catalysis triose include 1,3-Dihydroxyacetone (DHA) and glyceraldehyde (GLY) be converted into efficiently lactic acid or
Lactate, shows excellent isomerization activity and selectivity during catalysis.
The present invention compared with prior art, has the advantage that
The present invention provides a kind of just can be catalyzed the catalyst that triose Efficient Conversion is lactic acid or lactate, catalysis in room temperature
Agent can be reused, and has excellent isomerization activity and selectivity.
Accompanying drawing explanation
Fig. 1 is the XRD of the catalyst that embodiment 1 obtains.
Detailed description of the invention
With specific embodiment, technical scheme is described below, but protection scope of the present invention is not limited to this:
Molecular sieve used in following example is H-USY molecular sieve, and Si/Al is 3.2.
Embodiment 1
H-USY molecular sieve, in 8 mol/L salpeter solutions, with liquid-solid ratio 25 mL/g, at 85 DEG C of dealumination treatment 8 h, so
Rear filtration, wash, dry.Molecular sieve after dealuminzation is surveyed through Holland's Pa Nake Philips Magix type Xray fluorescence spectrometer
Fixed, Si/Al ratio is 50.7.
With SnCl4·5H2O is Sn source, by solid liposome nanoparticle method, and will molecular sieve after dealuminzation and SnCl4·5H2O
Mixed grinding, the Sn(of introducing 2.0% is with molecular sieve Mass Calculation), sample drying, roasting, obtain triose isomerization catalyst.
This catalyst PANalytical X Pert PRO powder x-ray diffraction measures its crystal phase structure, measures bar
Part: Cu target, voltage 40 kV, electric current 40 mA.X-ray diffractogram is as shown in Figure 1, it was demonstrated that gained catalyst maintains USY molecule
The crystal structure of sieve.
Application:
Take above-mentioned catalyst 0.133 g, methyl alcohol 5 mL, C3H6O3 (DHA) 0.116 g join reactor
In, in 25oC reacts 24 h, and obtaining DHA conversion ratio is 100%, and methyl lactate (MLA) yield is 99%.
Embodiment 2
In addition to replacing salpeter solution with 2 mol/L oxalic acid solutions, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 99%.
Embodiment 3
In addition to replacing salpeter solution with 2 mol/L edta solutions, remaining obtains triose isomery with embodiment 1
Change catalyst.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 96%.
Embodiment 4
In addition to replacing salpeter solution with 8 mol/L HCl solution, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 97%.
Embodiment 5
In addition to replacing salpeter solution with 2 mol/L citric acid solutions, remaining obtains triose isomerization catalytic with embodiment 1
Agent.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 84%.
Embodiment 6
Except using SnBr4Replace SnCl4·5H2Outside O, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 98%.
Embodiment 7
Except using SnSO4Replace SnCl4·5H2Outside O, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 93%.
Embodiment 8
Except using SnCl2·2H2O replaces SnCl4·5H2Outside O, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 99%.
Embodiment 9
Except using Sn (OAc)2Replace SnCl4·5H2Outside O, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 99%.
Embodiment 10
Except using SnC2O4Replace SnCl4·5H2Outside O, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 82%.
Embodiment 11
Except replacing SnCl with dimethylammonium chloride tin4·5H2Outside O, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 99%.
Embodiment 12
In addition to Sn content is 0.5%, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 90%.
Embodiment 13
In addition to Sn content is 5%, remaining obtains triose isomerization catalyst with embodiment 1.
This catalyst is catalyzed DHA under reaction condition same as in Example 1 and converts, and obtaining DHA conversion ratio is 100%,
MLA yield is 94%.
Embodiment 14
Catalyst 0.133 g prepared by Example 1, methyl alcohol 5 mL, DHA 0.116 g join in reactor, in
40 oC reacts 5 h, and obtaining DHA conversion ratio is 100%, and MLA yield is 97%.
Embodiment 15
Except reaction temperature is 70oC, reaction time are outside 0.5 h, and remaining is with embodiment 14, obtain DHA conversion ratio and are
99%, MLA yield is 92%.
Embodiment 16
Except DHA mass be 0.928 g, the reaction time be in addition to 5 h, remaining is with embodiment 15, and obtaining DHA conversion ratio is 95%,
MLA yield is 65%.
Embodiment 17
In addition to replacing DHA with glyceraldehyde, remaining is with embodiment 16, and obtaining conversion of glyceraldehyde rate is 94%, and MLA yield is
63%。
Embodiment 18
In addition to reaction temperature is 90 DEG C, remaining is with embodiment 17, and obtaining conversion of glyceraldehyde rate is 96%, and MLA yield is 71%.
Embodiment 19
In addition to using the methyl alcohol in ethanol alternate embodiment 17, remaining is with embodiment 17, obtains conversion of glyceraldehyde rate and is
84%, ethyl lactate yield is 53%.
Embodiment 20
In addition to replacing methyl alcohol with water, remaining is with embodiment 16, and obtaining DHA conversion ratio is 90%, and lactate yield is 60%.
Embodiment 21
In addition to replacing methyl alcohol with ethanol, remaining is with embodiment 16, and obtaining DHA conversion ratio is 90%, and ethyl lactate yield is
60%。
Embodiment 22
Solid catalyst in embodiment 1, is separated by filtration from reaction solution, washs with methyl alcohol, 110oC is dried.Return
The catalytic performance receiving catalyst is investigated same as in Example 1, and DHA conversion ratio is 99%, and the yield of MLA is 94%.
Embodiment 23
Solid catalyst in embodiment 17, is separated by filtration from reaction solution, washs with methyl alcohol, 110 DEG C of drying.
The catalytic performance reclaiming catalyst is investigated identical with embodiment 17, and conversion of glyceraldehyde rate is 93%, and the yield of MLA is 64%.
Claims (2)
1. one kind is catalyzed the preparation method that triose is isomerized to the catalyst of lactic acid and lactate, it is characterised in that described catalysis
Agent is by the USY molecular sieve of FAU configuration through acid treatment, and after acid treatment dealuminzation, in USY molecular sieve, sial atomic molar ratio is not less than
40, acid is configured to the aqueous solution, adds USY molecular sieve according to the ratio adding 1g in every 20-30ml aqueous acid, stir bar
Under part, 80-90 DEG C processes 6-8 hour；The USY molecular sieve of FAU configuration uses solid liposome nanoparticle method to introduce gold through acid treatment dealuminzation
Belong to ion Sn2+Or Sn4+, introduce metal ion Sn2+Or Sn4+The precursor used is its halide, acetate, sulfate, oxalates
Or organotin；Metal ion Sn2+Or Sn4+Introduction volume is the 0.1-5.0% of molecular sieve quality.
2. the application of catalyst prepared by preparation method as claimed in claim 1, it is characterised in that described catalyst is used for
Lactic acid or lactate are prepared in triose conversion in water or alcohol, and reaction temperature is 20-90oC, the time is 0.5-24 h, and triose is at water
Or the mass percentage concentration in alcohol is 2-30%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106748750B (en) * | 2015-11-19 | 2020-05-19 | 中国石油化工股份有限公司 | Method for preparing lactic acid from hemicellulose in corn straws |
| CN105879902B (en) * | 2016-05-19 | 2018-09-21 | 郑州大学 | A kind of preparation method for the molecular sieve catalyst preparing lactic acid and lactate for sugared conversion |
| CN111253250B (en) * | 2018-11-30 | 2023-03-10 | 中国石油化工股份有限公司 | Method for preparing lactate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102266793A (en) * | 2011-06-21 | 2011-12-07 | 西北大学 | Catalyst for producing propylene and producing method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102266793A (en) * | 2011-06-21 | 2011-12-07 | 西北大学 | Catalyst for producing propylene and producing method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Oxidative dehydrogenation of propane on zeolite catalysts;A. Kubacka et al.;《Catalysis Today》;20001231;第61卷;第343-352页 * |
| Zeolite H-USY for the production of lactic acid and methyl lactate from C3-sugars;Ryan M. et al.;《Journal of Catalysis》;20091125;第269卷;第122-130页 * |
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